Monoazo disperse dyes containing a nitrophenyl group and a homophthalimide group

ABSTRACT

Dyes of the formula ##STR1## where X and Y, for example, can be hydrogen or halogen and R can be alkyl among other substituents. The dyes are derived from an O-nitroaniline diazo component and an N-substituted homophthalimide as coupling component. The dyes are greenish yellow to orange and give clear dyeings of good color strength and having good general fastness properties on polyesters, cellulose esters and in some cases also on polyamides. The fastness to light and the fastness to heat setting are excellent and may easily be influenced by the choice of substituents.

This application is a continuation of application Ser. No. 188,610,which was filed on Oct. 12, 1971, which application has been abandoned.

The invention relates to dyes having the general formula (I): ##STR2##in which

X denotes hydrogen, chlorine, bromine, cyano, methylsulfonyl, carboxyl,carbalkoxy, carbamoyl or N-substituted carbamoyl;

Y denotes hydrogen, chlorine, bromine, nitro, cyano, methylsulfonyl,phenylsulfonyl, methyl, methoxy, phenylazo, carboxyl, carbalkoxy,carbamoyl, N-substituted carbamoyl, acetyl, benzoyl, sulfonamido,N-substituted sulfonamido or alkylsulfonato; and

R denotes alkyl having one to eighteen carbon atoms, chloroalkyl orbromoalkyl having two or three carbon atoms, hydroxyalkyl having two tosix carbon atoms, alkoxyalkyl having a total of three to eleven carbonatoms, acyloxyalkyl having three to eighteen carbon atoms, carboxyalkylhaving two to six carbon atoms, carboxyalkyl having three to elevencarbon atoms, carbamoylalkyl having two to eleven carbon atoms,alkanoylaminoalkyl having three to nine carbon atoms, benzoylaminoalkylhaving nine to thirteen carbon atoms, cyanoalkyl having two to sixcarbon atoms, polyglycol or polythioglycol radicals having four to eightcarbon atoms and which may be etherified (with C₁ to C₄ alkyl) oresterified (with C₂ to C₃ alkanoyl) or radicals having the formula:##STR3##

wherein the ring A may bear from one to three substituents from theseries chlorine, bromine, fluorine, methyl, methoxy or trifluoromethyl;

n denotes the integer 2, 3 or 6; and

m denotes the integer 2 or 3.

Examples of carbalkoxy and N-substituted carbamoyl radicals for X and Yare:

carbomethoxy, carboethoxy, carbopropoxy, carbobutoxy,carbo-β-ethylhexoxy, carbo-β-hydroxyethoxy, carbo-ω-hydroxypentoxy,carbo-ω-hydroxyhexoxy, carbo-β-methoxyethoxy, carbo-β-butoxyethoxy,N-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl,N-butylcarbamoyl, N-β-ethylhexylcarbamoyl, N-β-hydroxyethylcarbamoyl,N-β-hydroxypropylcarbamoyl, N-γ-hydroxypropylcarbamoyl,N-β-methoxyethylcarbamoyl, N-γ-methoxypropylcarbamoyl,N-γ-butoxypropylcarbamoyl, N-γ-(β'-ethylhexoxy)-propylcarbamoyl,N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N,N-dipropylcarbamoyl,N,N-dibutylcarbamoyl, N-methyl-N-β-hydroxyethylcarbamoyl,N,N-di-β-hydroxyethylcarbamoyl, N-benzylcarbamoyl,N-phenylethylcarbamoyl, carboxylic pyrrolidido, carboxylic piperididoand carboxylic morpholido and also the radicals having the formula:

NH--C₂ H₄ OC₂ H₄ OH, ##STR4## NH--C₂ H₄ OC₂ H₄ OCH₃ and NH--C₂ H₄ OC₂ H₄OC₂ H₅.

Examples of Y are the corresponding sulfonamides and suitable sulfonicalkyl esters are the alkyl esters having one to four carbon atoms, thehydroxyalkyl esters having two or three carbon atoms and the alkoxyalkylesters having three to seven carbon atoms.

Examples of radical R are:

methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-hexyl,β-ethylhexyl, n-decyl, β-methylnonyl, stearyl, β-hydroxyethyl,β-methoxyethyl, γ-hydroxypropyl, β-hydroxypropyl, γ-methoxypropyl,γ-ethoxypropyl, γ-(β-ethylhexoxy)-propyl, γ-acetoxypropyl,γ-propionyloxypropyl, benzoyloxyethyl, benzoyloxypropyl,methoxyacetoxypropyl, α-methyl-β-hydroxypropyl,β-methyl-β-hydroxypentyl, ω-hydroxyhexyl, carboxymethyl orcarboxypropyl, ethoxycarbonylmethyl, methoxycarbonylpropyl,dimethylaminocarbonylmethyl, butylaminocarbonylmethyl,phenylaminocarbonylpropyl, carboxyethyl, carboxypentyl,methoxycarbonylethyl, ethoxycarbonylpentyl, diethylaminocarbonylethyl,β-ethylhexylaminocarbonylethyl, phenylaminocarbonylpentyl,acetylaminoethyl, propionylaminoethyl, acetylaminopropyl,acetylaminobutyl, propionylaminobutyl, benzoylaminobutyl,acetylaminohexyl, ω-cyanopentyl, ω-cyanohexyl,β-(β'-hydroxyethoxy)-ethyl, β-(β'-acyloxyethoxy)ethyl and the radicalshaving the formulae:

--C₂ H₄ S--C₂ H₄ OH, --C₂ H₄ S--C₂ H₄ OCOC₆ H₅, --C₂ H₄ SC₂ H₄ OCOC₂ H₅,##STR5##

Dyes having the formula (I) are greenish yellow to orange and give cleardyeings of good color strength and having good general fastnessproperties on polyesters, cellulose esters and in some cases also onpolyamides. The good fastness to light and the fastness to heat settingare particularly noteworthy and they may easily be influenced by thechoice of substituents.

For the production of the new dyes, diazo compounds of amines having thegeneral formula (II): ##STR6## may be reacted with coupling componentshaving the general formula (III): ##STR7## where X, Y and R have themeanings given above.

Examples of compounds having the formula (II) are:

2-nitroaniline, 2,4-dinitroaniline, 4-chloro-2-nitroaniline,4-bromo-2-nitroaniline, 2-nitroaniline-4-carboxylic acid and its estersand amides, 4-acyl-2-nitroanilines, 2-nitroaniline-4-methylsulfone,2-nitroaniline-4-phenylsulfone and its derivatives bearing one or moreradicals such as halogen, methyl or methoxy in its phenyl radical,2-nitroaniline-4-sulfonic esters, 2-nitroaniline-4-sulfonamide,4-methyl-2-nitroaniline, 2-nitroaniline-6-carboxylic acid and its estersand amides, 2,4-dinitroaniline-6-carboxylic acid and its esters andamides and 4-phenylazo-2-nitroaniline.

When X or Y denotes carbalkoxy or unsubstituted or substitutedcarbamoyl, it may be advantageous to prepare these dyes by reaction of acompound having the formula (IV): ##STR8## in which either X or Ydenotes the COOH group or a negative derivative thereof, for example--COCl or --COBr, with the appropriate alcohol or amine.

Dyes having the formula (I) in which R denotes acyloxyalkyl, haloalkylor arylaminocarbonyloxyalkyl (urethane) are advantageously prepared fromthe corresponding hydroxyalkyl dyes by reaction with an acid halide,acid anhydride, phosphorus halide or aryl isocyanate.

All the said methods of production are known in principle from theliterature and the reactions proceed analogously.

Dyes having the general formula (Ia): ##STR9## in which

Y¹ denotes hydrogen, chlorine, carboalkoxy or N-substituted carbamoyl;and

R¹ denotes alkyl having one to four carbon atoms, ω-hydroxyalkyl,aroyloxyalkyl, arylaminocarbonyloxyalkyl or alkanoylaminoalkyl andwherein the

alkyl chain of the substituted alkyl radicals may be interrupted byoxygen atoms are of particular industrial importance.

The following Examples illustrate the invention. Parts and percentagesare by weight unless stated otherwise.

EXAMPLE 1

A solution of 27.6 parts of 2-nitroaniline in 75 parts of acetic acid ispoured into a mixture of 150 parts of water and 75 parts of concentratedhydrochloric acid. 200 parts of ice is added and diazotization iscarried out by dripping in a solution of 15 parts of sodium nitrite in35 parts of water. The whole is stirred for another two hours at 0° to5° C. and excess nitrate is destroyed by adding sulfamic acid. Thediazonium salt solution is stirred at 0° to 5° C. into a solution of 41parts of N-(β-hydroxyethyl)-homophthalimide in 100 parts of water and100 parts of dimethylformamide. The dye is precipitated as a yellowsolid. It is stirred for another two hours at 0° to 5° C. and for fourhours at room temperature and suction filtered, washed with water anddried. 65 parts of the dye having the constitution (R=--CH₂ --CH₂ --OH):##STR10## is obtained which dyes polyester and polyamide fibers andfabrics greenish yellow shades having good fastness to light anddry-heat pleating and setting.

Similar dyes are obtained from diazotized 2-nitroaniline and thesubstituted homophthalimides characterized by R in the following Table:

    __________________________________________________________________________    Example                                                                                 R            Shade   Material dyed                                  __________________________________________________________________________          ##STR11##        greenish yellow                                                                       polyester                                      3    CH.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3                                                          "       "                                              4    CH.sub.2 CH.sub.2 CH.sub.2 NHCOC.sub.2 H.sub.5                                                  "       "                                              5    CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.4 H.sub.5                                                     "       "                                              6    CH.sub.2 COOH     "       polyamide                                      7    CH.sub.2 CONH(CH.sub.2).sub.3 OCH.sub.3                                                         "       polyester                                      8    CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH                                        "       "                                              9    CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CN                                                 "       "                                              10   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                         "       "                                              11   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCOCH.sub.3                                                "       "                                              12                                                                                  ##STR12##        "       "                                              13                                                                                  ##STR13##        "       "                                              14                                                                                  ##STR14##        "       "                                              __________________________________________________________________________

EXAMPLE 15

A solution of 34.5 parts of 4-chloro-2-nitroaniline in 100 parts ofacetic acid is poured onto a mixture of 150 parts of concentratedhydrochloric acid and 150 parts of ice. Then, while stirring, a solutionof 15 parts of sodium nitrite in 35 parts of water is run in anddiazotization is completed by stirring for another four hours at 0° to5° C. After excess nitrite has been destroyed, the diazonium saltsolution is introduced in portions while stirring into a solution of43.8 parts of N-(γ-hydroxypropyl)-homophthalimide in 40 parts of aceticacid and 240 parts of water which is kept at +5° C. Stirring iscontinued for another four hours at 5° to 10° C. and the dye suctionfiltered, washed with water and dried. 76 parts of the dye having theformula (R=--CH₂ --CH₂ --CH₂ --OH): ##STR15## is obtained in the form ofan orange powder. It dyes fibers and fabrics of polyesters full, neutralyellow shades having excellent fastness to light and dry-heat pleatingand setting.

Other Examples of dyes having Y denoting Cl in formula (I) are:

    ______________________________________                                        Ex-                                Materials                                  ample      R               Shade   dyed                                       ______________________________________                                        16    CH.sub.3             yellow  polyester                                  17                                                                                   ##STR16##           "       "                                          18    (CH.sub.2).sub.17 CH.sub.3                                                                         "       "                                          19    CH.sub.2 CH.sub.2 OH "       "                                          20    CH.sub.2 CHOHCH.sub.3                                                                              "       "                                          21                                                                                   ##STR17##           "       "                                          22    CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                               "       "                                          23    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                            "       "                                          24    CH.sub.2 CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                      "       "                                          25    CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                        "       "                                          26    CH.sub.2 CON(C.sub.2 H.sub.5).sub.2                                                                "       "                                          27    CH.sub.2 CON(CH.sub.2 CH.sub.2 OH).sub.2                                                           "       "                                          28    CH.sub.2 CH.sub.2 COOH                                                                             "       polyamide                                  29    CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                                     "       polyester                                  30    CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                   "       "                                          31    CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CN                                           "       "                                          32                                                                                   ##STR18##           "       "                                          33                                                                                   ##STR19##           "       "                                          34                                                                                   ##STR20##           "       "                                          35                                                                                   ##STR21##                                                              ______________________________________                                    

EXAMPLE 36

30.4 parts of 4-methyl-2-nitroaniline is dissolved in a mixture of 50parts of acetic acid, 75 parts of concentrated hydrochloric acid and 150parts of water. Diazotization is carried out by dripping in a solutionof 15 parts of sodium nitrite in 35 parts of water at 0° to 5° C. andstirring for another two hours at this temperature. Excess nitrite isdestroyed with sulfamic acid and the diazonium salt solution is drippedinto a solution of 49.4 parts of N-(β-acetoxyethyl)-homophthalimide in100 parts of acetic acid and 100 parts of water. The temperature is keptat about +5° C. by adding ice. The whole is stirred for another fourhours at about +5° C. and for another sixteen hours at room temperatureand then the dye is suction filtered, washed with water and dried. 73parts of the dye having the formula (R=CH₂ --CH₂ OCOCH₃): ##STR22## isobtained in the form of a reddish yellow powder.

Reddish yellow dyeings having good fastness to light and dry-heatpleating and setting are obtained therewith on polyesters.

The following dyes are obtained with the same diazo component with othersubstituted homophthalimides:

    ______________________________________                                        Ex-                                Material                                   ample      R           Shade       dyed                                       ______________________________________                                        37    CH.sub.2 CH.sub.3                                                                              reddish yellow                                                                            polyester                                  38    CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                            "           "                                          39    CH.sub.2 CH.sub.2 OH                                                                           "           polyamide                                  40    CH.sub.2 CH.sub.2 CH.sub.2 OH                                                                  "           polyester                                  41    CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                           "           "                                          42                                                                                   ##STR23##       "           "                                          43    CH.sub.2 CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                  "           "                                          44    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                        "           "                                          45    CH.sub.2 CH.sub.2 NHCOC.sub.2 H.sub.5                                                          "           "                                          ______________________________________                                    

EXAMPLE 46

36.6 parts of 2,4-dinitroaniline is introduced at 5° to 10° C. into asolution of 15 parts of sodium nitrite in 350 parts of 85% sulfuricacid. After stirring for four hours at this temperature, the sulfuricacid solution is poured onto 1000 parts of ice and the excess nitrite isdestroyed with sulfamic acid. Then a solution of 35 parts ofN-methylhomophthalimide in 250 parts of dimethylformamide is dripped inand the acid is neutralized by adding 150 parts of 25% ammonia solutionin portions. The whole is stirred for another two hours at 10° C. andfor sixteen hours at room temperature, suction filtered, washed withwater and dried. 65 parts of the dye having the formula (R=CH₃):##STR24## is obtained. Neutral yellow dyeings having good light fastnessand thermal stability are obtained with the dye on polyesters.

The following dyes are obtained analogously with the same diazocomponent:

    ______________________________________                                        Ex-                                                                           am-                                 Material                                  ple       R                 Shade   dyed                                      ______________________________________                                        47   CH.sub.2 CH.sub.2 CH.sub.3                                                                           yellow  polyester                                 48   (CH.sub.2).sub.9 CH.sub.3                                                                            "       "                                         49   CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                        "       "                                         50   CH.sub.2 CH.sub.2 CH.sub.2 OH                                                                        "       "                                         51                                                                                  ##STR25##             "       "                                         52   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NHCOCH.sub.3                                   "       "                                         53                                                                                  ##STR26##             "       "                                         54                                                                                  ##STR27##             "       "                                         ______________________________________                                    

EXAMPLE 55

The 2,4-dinitroaniline in Example 46 is replaced by 47.6 parts of thebutyl ester of 2-nitroaniline-4-carboxylic acid and otherwise theprocedure of Example 46 is adopted. 76 parts of a yellow dye having theformula: ##STR28## (R=CH₃ ; R'=OC₄ H₉) is obtained which gives greenishyellow dyeings having very good fastness to light and dry-heat pleatingand setting on polyesters.

The following dyes are prepared analogously:

    __________________________________________________________________________                                            Material                              Example                                                                             R                R'       Shade   dyed                                  __________________________________________________________________________    56   CH.sub.3     OCH.sub.2 CH.sub.2 OH                                                                       greenish yellow                                                                       polyester                             57   CH.sub.3                                                                                    ##STR29##    "       "                                     58   CH.sub.3     OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH                                                     "       "                                     59   CH.sub.3     NHC.sub.3 H.sub.9                                                                           "       "                                     60   CH.sub.3                                                                                    ##STR30##    "       "                                     61   CH.sub.3     NHCH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                               "       "                                     62   CH.sub.3     NHCH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                         "       "                                     63   CH.sub.3     N(C.sub.4 H.sub.9).sub.2                                                                    "       "                                     64   CH.sub.3                                                                                    ##STR31##    "       "                                     65   CH.sub.3     NHCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.                                                       " OH    "                                     66   CH.sub.3                                                                                    ##STR32##    "       "                                     67   C.sub.2 H.sub.5                                                                            OC.sub.2 H.sub.5                                                                            "       "                                     68   C.sub.2 H.sub.5                                                                            NHC.sub.2 H.sub.5                                                                           "       "                                     69   CH.sub.2 CH.sub.2 OH                                                                       OC.sub.4 H.sub.9                                                                            "       "                                     70   CH.sub.2 CH.sub.2 CH.sub.2 OH                                                              OC.sub.2 H.sub.5                                                                            "       "                                     71   CH.sub.2 COOH                                                                              OC.sub.2 H.sub.5                                                                            yellow  polyamide                             72   CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                       OC.sub.4 H.sub.9                                                                            greenish yellow                                                                       polyester                             73   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                    OC.sub.2 H.sub.5                                                                            "       "                                     74                                                                                  ##STR33##   OC.sub.4 H.sub.9                                                                            "       "                                     75   CH.sub.2 CH.sub.2 OH                                                                       CH.sub.3      yellow  "                                     76   CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                CH.sub.3      "       "                                     77   C.sub.4 H.sub.9                                                                            C.sub.6 H.sub.5                                                                             "       "                                     78   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                    C.sub.6 H.sub.5                                                                             "       "                                     79   (CH.sub.2).sub.6 OH                                                                        C.sub.6 H.sub.5                                                                             "       "                                     80   (CH.sub.2).sub.5 CN                                                                        C.sub.6 H.sub.5                                                                             "       "                                     81                                                                                  ##STR34##                                                                                  ##STR35##    "       "                                     82   (CH.sub.2).sub.4 NHCOCH.sub.3                                                               ##STR36##    "       "                                     __________________________________________________________________________

EXAMPLE 83

36.4 parts of 3-nitro-4-aminobenzoic acid is dissolved in 300 parts of3% caustic soda solution. 15 parts of sodium nitrite, 250 parts of iceand 80 parts of concentrated hydrochloric acid are added to the solutionin this sequence and the whole is stirred for another four hours at 0°to 5° C. Excess nitrite is then destroyed and the diazonium saltsolution is dripped into a solution of 41 parts ofN-(β-hydroxyethyl)-homophthalimide in 250 parts of 25% acetic acid. Theacid is then neutralized by batchwise addition of 75 parts ofconcentrated ammonia solution. The whole is stirred for two hours at 5°C. and for sixteen hours at room temperature, suction filtered, washedwith water and dried. 77 parts of the dye having the formula (R=--CH₂--CH₂ --OH): ##STR37## is obtained in the form of a brown powder.

The dye gives yellow shades on polyamide fibers and cloth when appliedfrom an aqueous liquor; the dyeings have good fastness to light anddry-heat pleating and setting.

Dyes having similar tinctorial properties are obtained when thehomophthalimides characterized by R in the following Table are used ascoupling components:

    ______________________________________                                                                           Material                                   Example                                                                                   R              Shade   dyed                                       ______________________________________                                        84     CH.sub.3            yellow  polyamide                                  85     CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      "       "                                          86     CH.sub.2 CH.sub.2 CH.sub.2 OH                                                                     "       "                                          87     CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                       "       "                                          88     CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                     "       "                                          89     CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                           "       "                                          90                                                                                    ##STR38##          "       "                                          91     CH.sub.2 COOH       "       "                                          92     CH.sub.2 CH.sub.2 COOH                                                                            "       "                                          93     CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 COOH                                                 "       "                                          ______________________________________                                    

EXAMPLE 94

42.0 parts of ethyl 2-amino-3-nitrobenzoate is introduced at 0° to 5° C.into a solution of 15 parts of sodium nitrite in 400 parts of 85%sulfuric acid. The whole is stirred for four hours at 5° C. Thediazonium solution is poured onto 1500 parts of ice and the excessnitrite is destroyed by adding sulfamic acid. A solution of 41.0 partsof N-(β-hydroxyethyl)-homophthalimide in 100 parts of dimethylformamideand 100 parts of water is then dripped in while stirring and coolingwith ice. The acid is gradually neutralized with aqueous ammonia. Thewhole is stirred for another two hours at 5° C. and for twelve hours atroom temperature, suction filtered, washed with water and dried. 77parts of the dye having the formula (R=--CH₂ --CH₂ --OH; R'=--OC₂ H₅):##STR39##

The dye gives greenish yellow dyeings having good fastness to light anddry-heat pleating and setting on polyesters.

The dyes set out in the following Table are obtained analogously:

    __________________________________________________________________________                                              Material                            Example                                                                                R             R'         Shade   dyed                                __________________________________________________________________________     95  CH.sub.3     OCH.sub.2 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 CH.sub.3                                        greenish yellow                                                                       polyester                            96  CH.sub.2 CH.sub.2 CH.sub.2 OH                                                              OC.sub.4 H.sub.9                                                                              "       "                                    97  CH.sub.2 CH.sub.2 CH.sub.2 OH                                                              NHC.sub.4 H.sub.9                                                                             "       "                                    98   "           NHCH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                 "       "                                    99   "           N(CH.sub.3).sub.2                                                                             "       "                                   100   "                                                                                          ##STR40##      "       "                                   101  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                    OC.sub.2 H.sub.5                                                                              "       "                                   102   "           N(C.sub.2 H.sub.5).sub.2                                                                      "       "                                   103   "           C.sub.6 H.sub.4 CH.sub.3 (p)                                                                  "       "                                   104  CH.sub. 2 CH.sub.2 OH                                                                      OH              "       polyamide                           105  CH.sub.2 CH.sub.2 CH.sub.2 OH                                                              OH              "       "                                   106  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                    OH              "       "                                   107  CH.sub.2 COOH                                                                              OH              "       "                                   108  CH.sub.2 CH.sub.2 COOH                                                                     OH              "       "                                   109  (CH.sub.2).sub.5 COOH                                                                      OH              "       "                                   __________________________________________________________________________

EXAMPLE 110

The ethyl 2-amino-3-nitrobenzoate of Example 94 is replaced by 51 partsof ethyl 2-amino-3,5-dinitrobenzoate. 86.4 parts of the dye having theformula (R=--CH₂ --CH₂ --OH; R'=--C₂ H₅): ##STR41## is obtained. It dyesfibers and cloth of polyesters greenish yellow shades having goodfastness to light and dry-heat pleating and setting.

The following dyes are obtained analogously to Example 110:

    __________________________________________________________________________    Example                                                                            R            R'            Shade                                                                              Material dyed                            __________________________________________________________________________    111  --CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                              --OC.sub.2 H.sub.5                                                                          greenish                                                                           polyester                                                                yellow                                        112  --CH.sub.2 CH.sub.2 OH                                                                     --OC.sub.4 H.sub.9                                                                          greenish                                                                           "                                                                        yellow                                        113  --(CH.sub.2).sub.6 OH                                                                      --OC.sub.4 H.sub.9                                                                          greenish                                                                           "                                                                        yellow                                        114  --CH.sub.2 CH.sub.2 CH.sub.2 OH                                                            --NHCH.sub.2 CH.sub.2 --CH.sub.2 OCH.sub.3                                                  greenish                                                                           "                                                                        yellow                                        115  --CH.sub.2 CH.sub.2 CH.sub.2 OH                                                            --N(C.sub.4 H.sub.9).sub.2                                                                  greenish                                                                           "                                                                        yellow                                        116  --CH.sub.2 CH.sub.2 OH                                                                     --NHCH.sub.2 CH.sub.2 CH.sub.2 OH                                                           greenish                                                                           "                                                                        yellow                                        117  --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                  --NHCH.sub.3  greenish                                                                           "                                                                        yellow                                        118  --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                  --N(CH.sub.3).sub.2                                                                         greenish                                                                           "                                                                        yellow                                        __________________________________________________________________________

EXAMPLE 119

46.2 parts of 2-nitroaniline-4-sulfonic-N-methylamide is introduced into300 parts of nitrosylsulfuric acid (equivalent to 15 parts of sodiumnitrite) while cooling with ice. The whole is stirred for four hours at0° to 5° C. The mixture is then poured onto 1200 parts of ice and alittle sulfamic acid. A solution of 46.6 parts ofN-(γ-methoxypropyl)-homophthalimide in 400 parts of 50% acetic acid isthen dripped in. Coupling is completed by neutralization to pH about 5with aqueous ammonia solution and the whole is stirred for some hours,suction filtered, washed with water and dried. 89 parts of the dyehaving the formula (R=--CH₂ --CH₂ --CH₂ --OCH₃ ; R'=--NHCH₃): ##STR42##is obtained. Greenish yellow dyeings which are distinguished by verygood fastness to light and thermal stability are obtained with the dyeon polyester threads, filaments and cloth from an aqueous liquor.

The following dyes are obtained by varying the radicals R and R' in thediazo component and coupling component:

    __________________________________________________________________________                                                 Material                         Example                                                                                 R               R'         Shade   dyed                             __________________________________________________________________________    120  CH.sub.3        NHCH.sub.2 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3                                CH.sub.3        greenish yellow                                                                       polyester                        121  CH.sub.3        N(C.sub.4 H.sub.9).sub.2                                                                      "       "                                122  CH.sub.2 CH.sub.2 OH                                                                          NHCH.sub.3      "       "                                123  CH.sub.2 CH.sub.2 CH.sub.2 OH                                                                  ##STR43##      "       "                                124  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                        ##STR44##      "       "                                125  CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                          OC.sub.4 H.sub.9                                                                              "       "                                126  (CH.sub.2).sub.9 CH.sub.3                                                                     CH.sub.3        "       "                                127  CH.sub.2 CH.sub.2 OH                                                                          CH.sub.3        "       "                                128                                                                                 ##STR45##      CH.sub.3        "       "                                129                                                                                 ##STR46##      CH.sub.3        "       "                                130  CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NHCOC.sub.2 H.sub.5                                       CH.sub.3        "       "                                131  CH.sub.2 CHOHCH.sub.3                                                                         C.sub.6 H.sub.5 "       "                                132                                                                                 ##STR47##      C.sub.6 H.sub.5 "       "                                133  CH.sub.2 CH.sub.2 OH                                                                          C.sub.6 H.sub.4CH.sub.3 (p)                                                                   "       "                                134  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                       C.sub.6 H.sub.4 OCH.sub.3 (p)                                                                 "       "                                135  (CH.sub.2).sub.6 OH                                                                           C.sub.6 H.sub.4 Cl(p)                                                                         "       "                                __________________________________________________________________________

EXAMPLE 136

48.4 parts of 3-nitro-4-aminoazobenzene is dissolved in 300 parts ofwarm glacial acetic acid and the solution is poured onto a mixture of100 parts of concentrated hydrochloric acid and 400 parts of ice.Diazotization is then carried out by dripping in a solution of 15 partsof sodium nitrite in 30 parts of water and stirring for another fourhours at 0° to 5° C. Excess nitrite is then destroyed with sulfamic acidand the diazonium salt solution is dripped while cooling into a solutionof 35.0 parts of N-methylhomophthalimide in 150 parts ofdimethylformamide and 150 parts of 20% acetic acid. The temperature iskept at 0° to 5° C. for another two hours by adding ice andneutralization with aqueous ammonia is carried out at the same time.After another sixteen hours at room temperature, the dye is suctionfiltered, washed with water and dried. 80.7 parts of the dye having theformula (R=--CH₃): ##STR48## is obtained in the form of a brown powder.

The dye gives golden yellow shades having good color strength and verygood fastness to light and dry-heat pleating and setting on polyestermaterial.

The following dyes are obtained analogously:

    ______________________________________                                                                            Material                                  Example                                                                              R                Shade       dyed                                      ______________________________________                                        137    --C.sub.2 H.sub.5                                                                              golden yellow                                                                             polyester                                 138    --CH.sub.2 CH.sub.2 OH                                                                         "           "                                         139    --CH.sub.2 CH.sub.2 CH.sub.2 OH                                                                "           "                                         140    --CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                         "           "                                         141    --CH.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3                                                       "           "                                         ______________________________________                                    

EXAMPLE 142

A mixture of 200 parts of hexanediol-(1,6), 20 parts ofp-toluenesulfonic acid and 36.8 parts of the dye from Example 84 isstirred for eight hours at 130° C. After cooling, the whole is dilutedwith 300 parts of methanol and the precipitate is suction filtered,washed with methanol and dried. 41 parts of a dye having the formula:##STR49## (R=CH₃ ; R'=--O(CH₂)₆ OH) is obtained. It gives greenishyellow dyeings having very good fastness to light and dry-heat pleatingand setting on polyesters.

The following dyes are prepared analogously:

    __________________________________________________________________________                                        Material                                  Example                                                                             R           R'        Shade   dyed                                      __________________________________________________________________________    143  CH.sub.3                                                                              O(CH.sub.2).sub.4 CH.sub.3                                                                   greenish yellow                                                                       polyester                                 144  CH                                                                                     ##STR50##     "       "                                         145  C.sub.2 H.sub.5                                                                       O(CH.sub.2).sub.5 OH                                                                         "       "                                         146  C.sub.2 H.sub.5                                                                       OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                              "       "                                         147  C.sub.4 H.sub.9                                                                       O(CH.sub.2).sub.2 OH                                                                         "       "                                         148  C.sub.4 H.sub.9                                                                       O(CH.sub.2).sub.4 OH                                                                         "       "                                         149  (CH.sub.2).sub.3 OCH.sub.3                                                            O(CH.sub.2).sub.3 CH.sub.3                                                                   "       "                                         150  (CH.sub.2).sub.3 OCH.sub.3                                                            O(CH.sub.2).sub.2 OH                                                                         "       "                                         151  (CH.sub.2).sub.3 OCH.sub.3                                                            O(CH.sub.2).sub.2 OCH.sub.3                                                                  "       "                                         __________________________________________________________________________

EXAMPLE 152

36.8 parts of the dye of Example 84 is suspended in 375 parts ofchlorobenzene and after 1 part of dimethylformamide and 15 parts ofthionyl chloride have been added the whole is stirred for eight hours ona boiling waterbath. After cooling, the precipitate is suction filtered,washed with benzene and dried. 34.8 parts of the corresponding acidchloride (R=CH₃ ; R'=Cl) is obtained in the form of yellow crystalshaving a melting point of 272° C. to 273° C. (with decomposition) and achlorine content of 9.5% (calculated: 9.1%).

200 parts of pentanediol-(1,5), 10 parts of pyridine and 38.65 parts ofthe acid chloride thus obtained are stirred for two hours at 100° to120° C. After cooling, the whole is diluted with 300 parts of methanoland the precipitate is suction filtered, washed with methanol and dried.40.1 parts of the dye having the formula (see Example 142) (R=CH₃ ;R'=--O(CH₂)₅ OH) is obtained. It dyes fibers and cloth of polyestersgreenish yellow shades having excellent fastness to light and dry-heatpleating and setting.

EXAMPLE 153

38.65 parts of the acid chloride prepared according to Example 152 isintroduced into 200 parts of dimethylformamide, 17 parts of pyrrolidineis added and the whole is stirred for two hours at 120° C., diluted with100 parts of 50% aqueous methanol, allowed to cool, suction filtered,washed with water and dried. 40.1 parts of a dye is obtained which isidentical chemically and tinctorially with the dye obtained according toExample 64.

EXAMPLE 154

A mixture of 350 parts of chlorobenzene, 15 parts of thionyl chloride, 1part of dimethylformamide and 42.4 parts of the dye from Example 85 iskept at 95° to 100° C. for six hours. 50 parts is distilled off at apressure of about 50 mm so that excess thionyl chloride is removed. Aweak current of gaseous dimethylamine is passed into the remainingsolution of the acid chloride at 100° C. for about two hours and thenthe reaction mixture is subjected to steam distillation. The dye whichafter this is present as an aqueous suspension is suction filtered,washed with water and dried at 50° C. at subatmospheric pressure. 39parts of a compound (R=--C₅ H₁₁ ; ##STR51## is obtained which exhibitstinctorial properties on polyesters which are similar to those of thedye of Example 153.

Dyes having the formula according to Example 142 which are characterizedin the following Table by R and R' are obtained analogously to theprocedure described in Examples 152 to 154:

    __________________________________________________________________________                                             Material                             Example                                                                             R              R'          Shade   dyed                                 __________________________________________________________________________    155  CH.sub.3   OCH.sub.3        greenish yellow                                                                       polyester                            156  "          OCH.sub.2 CH.sub.2 OH                                                                          "       "                                    157  "          OCH.sub.2 CH.sub.2 OCH.sub.3                                                                   "       "                                    158  "                                                                                         ##STR52##       "       "                                    159  "          OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                       "       "                                    160  "          OCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 OH                                                       "       "                                    161  "          OCH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 OH                                                        "       "                                    162  "          OCH.sub.2 C(C.sub.2 H.sub.5).sub.2 CH.sub.2 OH                                                 "       "                                    163  "          OCH.sub.2 C(CH.sub.3).sub.2 CHOH(CH.sub.2).sub.2 CH.sub.3                                      "       "                                    164  "          NHCH.sub.3       "       "                                    165  "          NHC.sub.2 H.sub.5                                                                              "       "                                    166  "          NHC.sub.4 H.sub.9                                                                              "       "                                    167  "          NHCH.sub.2 CH.sub.2 OH                                                                         "       "                                    168  "          NHCH.sub.2 CHOHCH.sub.3                                                                        "       "                                    169  "          NH(CH.sub.2).sub.3 OH                                                                          "       "                                    170  "          NH(CH.sub.2).sub.6 OH                                                                          "       "                                    171  "                                                                                         ##STR53##       "       "                                    172  "          NH(CH.sub.2).sub.6 CN                                                                          "       "                                    173  "          NH(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH                                                        "       "                                    174  "          NHCH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                            "       "                                    175  "                                                                                         ##STR54##       "       "                                    176  "                                                                                         ##STR55##       "        "                                   177  "          N(CH.sub.3).sub.2                                                                              "       "                                    180  "          N(C.sub.2 H.sub.5).sub.2                                                                       "       "                                    181  "          N(C.sub.3 H.sub.7).sub.2                                                                       "       "                                    182  "          N(C.sub.4 H.sub.9).sub.2                                                                       "       "                                    183  "                                                                                         ##STR56##       "       "                                    184  "                                                                                         ##STR57##       "       "                                    185  CH.sub.3                                                                                  ##STR58##       "       "                                    186  "                                                                                         ##STR59##       "       "                                    187  "                                                                                         ##STR60##       "       "                                    188  "                                                                                         ##STR61##       "       "                                    189  C.sub.2 H.sub.5                                                                          OC.sub.2 H.sub.5 "       "                                    190  "          OCH.sub.2 CH.sub.2 OH                                                                          "       "                                    191  "          OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                       "       "                                    192  "          N(C.sub.4 H.sub.9).sub.2                                                                       "       "                                    193  "          NH(CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                            "       "                                    194  "          NH(CH.sub.2).sub.5 CN                                                                          "       "                                    195  "                                                                                         ##STR62##       "       "                                    196  "          NHCH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                            "       "                                    197  C.sub.4 H.sub.9                                                                          OCH.sub.3        "       "                                    198  "          OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH                                                        "       "                                    199  "          OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                       "       "                                    200  "           NHCH.sub.3      "       "                                    201  "          NHCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                         "       "                                    202  "          NHCH.sub.2 C.sub.6 H.sub.5                                                                     "       "                                    203  "          N(CH.sub.3).sub.2                                                                              "       "                                    204  "                                                                                         ##STR63##       "       "                                    205  "                                                                                         ##STR64##       "       "                                    206  CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     OC.sub.2 H.sub.5 "       "                                    207  "          OCH.sub.2 CH.sub.2 OH                                                                          "       "                                    208  "          O(CH.sub.2).sub.5 OH                                                                           "       "                                    209  "          NHCH.sub.2 CH.sub.2 OH                                                                         "       "                                    210  "                                                                                         ##STR65##       "       "                                    211  "          N(CH.sub.3).sub.2                                                                              "       "                                    212  CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                     N(CH.sub.2 CH.sub.2 OH).sub.2                                                                  "       " -213 "                                                                       "#"TR66##                           214  "                                                                                         ##STR67##       "       "                                    215  "                                                                                         ##STR68##       "       "                                    __________________________________________________________________________

EXAMPLE 216

35.4 parts of the dye from Example 1 and 30 parts of 2-ethylhexanoicacid anhydride are introduced into 250 parts of pyridine. The whole isboiled under reflux for one hour and then poured onto ice and excesshydrochloric acid. The deposited dye is suction filtered, washed withdilute hydrochloric acid and with water and dried. 44.5 parts of dye##STR69## is obtained which gives clear greenish yellow dyeings havinggood fastness to light and dry-heat pleating and setting on polyesters.

EXAMPLE 217

A mixture of 200 parts of dimethylformamide, 40.25 parts of the dye fromExample 15, 15.11 parts of triethylamine and 14.5 parts of benzoylchloride is stirred for two hours at 120° C. The whole is then pouredonto ice and worked up as described in Example 216. 49 parts of thecorresponding dye with R=--CH₂ --CH₂ --CH₂ --O--CO--C₆ H₅ is obtainedwhich dyes polyester material yellow shades. The dyeings have excellentfastness to light and dry-heat pleating and setting.

The dyes characterized in the following Table by their substituents areobtained analogously to the specified procedure:

    __________________________________________________________________________    Example                                                                               R                      Shade   Material dyed                          __________________________________________________________________________    Formula (I): X = Y = H                                                        218  (CH.sub.2).sub.2 OCOCH.sub.3                                                                            greenish yellow                                                                       polyester                              219  (CH.sub.2).sub.2 OCOCH.sub.2 OCH.sub.3                                                                  "       "                                      220  (CH.sub.2).sub.2 OCOC(CH.sub.3).sub.3                                                                   "       "                                      221  (CH.sub.2).sub.2 OCOC.sub.4 H.sub.9                                                                     "       "                                      222  (CH.sub.2).sub.2 OCOC.sub.6 H.sub.5                                                                     "       "                                      223  (CH.sub.2).sub.2 OCOCH.sub.2 C.sub.6 H.sub.5                                                            "       "                                      224                                                                                 ##STR70##                "       "                                      225                                                                                 ##STR71##                "       "                                      226                                                                                 ##STR72##                "       "                                      227                                                                                 ##STR73##                "       "                                      228  (CH.sub. 2).sub.3 OCOCH.sub.2 CH.sub.2 CH.sub.3                                                         "       "                                      229  (CH.sub.2).sub.3 OCOCH.sub.2 OCH.sub.3                                                                  "       "                                      230  (CH.sub.2).sub.3 OCOCH.sub.2 CH.sub.2 COOH                                                              "       "                                      231                                                                                 ##STR74##                "       "                                      232                                                                                 ##STR75##                                                               233                                                                                 ##STR76##                "       "                                      234                                                                                 ##STR77##                "       "                                      235  (CH.sub.2).sub.6 OCOC.sub.6 H.sub.5                                                                     "       "                                      236                                                                                 ##STR78##                "       "                                      237                                                                                 ##STR79##                "       "                                      238  (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OCOCCl.sub.3                                                         "       "                                      239   (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OCOC.sub.6 H.sub.5                                                  "       "                                      240                                                                                 ##STR80##                "       "                                      241                                                                                 ##STR81##                "       "                                      242                                                                                 ##STR82##                "       "                                      Formula (I): X = H Y = Cl                                                     243  (CH.sub.2).sub.2 OCOCH.sub.2 CH.sub.3                                                                   yellow  "                                      244  (CH.sub.2).sub.2 OCOCH.sub.2 OCH.sub.3                                                                  "       "                                      245  (CH.sub.2).sub.3 OCOCHCl.sub.3                                                                          "       "                                      246  (CH.sub.2).sub.2 OCOCH.sub.2 CH.sub.2 COOH                                                              "       "                                      247                                                                                 ##STR83##                "       "                                      248                                                                                 ##STR84##                "       "                                      249                                                                                 ##STR85##                "       "                                      250                                                                                 ##STR86##                "       "                                      251                                                                                 ##STR87##                "       "                                      252                                                                                 ##STR88##                "       "                                      253                                                                                 ##STR89##                "       "                                      254                                                                                 ##STR90##                "       "                                      255  (CH.sub.2).sub.3 OCOC(CH.sub.3).sub.3                                                                   "       "                                      256                                                                                 ##STR91##                "       "                                      257  (CH.sub.2 ).sub.3 OCOCCl.sub.3                                                                          "       "                                      258                                                                                 ##STR92##                "       "                                      259                                                                                 ##STR93##                "       "                                      260                                                                                 ##STR94##                "       "                                      261                                                                                 ##STR95##                "       "                                      262                                                                                 ##STR96##                "       "                                      263                                                                                 ##STR97##                "       "                                      264  (CH.sub.2).sub.6 OCOC.sub.6 H.sub.5                                                                     "       "                                      265                                                                                 ##STR98##                "       "                                      266                                                                                 ##STR99##                "       "                                      267  (CH.sub. 2).sub.2 O(CH.sub.2).sub.2 OCOCH.sub.2 OCH.sub.3                                               "       "                                      268  (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OCOCCl.sub.3                                                         "       "                                      269  (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OCOC.sub.6 H.sub.5                                                   "       "                                      270                                                                                 ##STR100##               "       "                                      271                                                                                 ##STR101##               "       "                                      272                                                                                 ##STR102##               "       "                                      Formula (I): X = H Y = CH.sub.3                                               273  (CH.sub.2).sub.3 OCO(CH.sub.3).sub.3                                                                    reddish yellow                                                                        "                                      274  (CH.sub.2).sub.3 OCOCH.sub.2 CH.sub.2 COOH                                                              "       "                                      275  (CH.sub.2).sub.3 OCOC.sub.6 H.sub.5                                                                     "       "                                      276                                                                                 ##STR103##               "       "                                      277                                                                                 ##STR104##               "       "                                      Formula (I): X = H Y = C.sub.6 H.sub.5NN                                      278  (CH.sub.2).sub.2 OCOCH.sub.3                                                                             golden yellow                                                                        "                                      279  (CH.sub.2).sub.2 OCOCH.sub.2 Cl                                                                          "      "                                      280  (CH.sub.2).sub.2 OCOC(CH.sub.3).sub.3                                                                    "      "                                      281                                                                                 ##STR105##                                                              __________________________________________________________________________

EXAMPLE 282

40.25 parts of the dye of Example 15, 14 parts of phenyl isocyanate and1 part of pyridine are introduced into 300 parts of o-dichlorobenzeneand heated to 150° to 160° C. The dye passes into solution. The whole iskept for four hours at 150° to 160° C. and during cooling is dilutedwith 50 parts of ethanol and 250 parts of cyclohexane. After standingovernight the yellow crystals are suction filtered, washed with methanoland dried. 38.9 parts of the corresponding dye (R=--CH₂ CH₂ CH₂ OCONHC₆H₅) is obtained which dyes polyester yellow shades. The dyeings havegood light fastness and resistance to contact heat.

The following dyes are prepared by the same procedure:

    __________________________________________________________________________    Example                                                                               R                 Shade   Material dyed                               __________________________________________________________________________    Formula (I): X = Y = H                                                        283  (CH.sub.2).sub.2 OCONHC.sub.6 H.sub.5                                                              greenish yellow                                                                       polyester                                   284                                                                                 ##STR106##          "       "                                           285                                                                                 ##STR107##          "       "                                           286                                                                                 ##STR108##          "       "                                           287  (CH.sub.2).sub.3 OCONHC.sub.6 H.sub.5                                                              "       "                                           288                                                                                 ##STR109##          "       "                                           289                                                                                 ##STR110##          "       "                                           290                                                                                 ##STR111##          "       "                                           291  (CH.sub.2).sub.6 OCONHC.sub.6 H.sub.5                                                              "       "                                           292  (CH.sub.2 ).sub.2 O(CH.sub.2).sub.2 OCONHC.sub.6 H.sub.5                                           "       "                                           293                                                                                 ##STR112##          "       "                                           294                                                                                 ##STR113##          "       "                                           Formula (I): X = H Y = Cl                                                     295  (CH.sub.2).sub.2 OCONHC.sub.6 H.sub.5                                                              yellow  "                                           296                                                                                 ##STR114##          "       "                                           297                                                                                 ##STR115##          "       "                                           298                                                                                 ##STR116##          "       "                                           299                                                                                 ##STR117##          "       "                                           300                                                                                 ##STR118##          "       "                                           301                                                                                 ##STR119##          "       "                                           302                                                                                 ##STR120##          "       "                                           303  (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OCONHC.sub.6 H.sub.5                                            "       "                                           304                                                                                 ##STR121##          "       "                                           305                                                                                 ##STR122##          "       "                                           306                                                                                 ##STR123##          "       "                                           Formula (I): X = H Y = CH.sub.3                                               307  (CH.sub.2).sub.2 OCONHC.sub.6 H.sub.5                                                              reddish yellow                                                                        "                                           308                                                                                 ##STR124##          "       "                                           309  (CH.sub.2 ).sub.3 OCONHC.sub.6 H.sub.5                                                             "       "                                           310                                                                                 ##STR125##          "       "                                           311  (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OCONHC.sub.6 H.sub.5                                            "       "                                           __________________________________________________________________________

EXAMPLE 312

A mixture of 300 parts of chlorobenzene, 35.4 parts of the dye fromExample 1 and 30 parts of phosphorus oxychloride is boiled under refluxfor four hours. The dye passes into solution. The whole is filteredwhile hot and 20 parts of methanol is added to the filtrate duringcooling of the same. The whole is then allowed to stand overnight, andthe dye which has separated in crystalline form is suction filtered,washed with methanol and dried. 28 parts of dye (R=--CH₂ CH₂ Cl) havinga chlorine content of 8.8% (calculated 9.5%) is obtained. The dye goesonto fibers and cloth of polyesters from an aqueous liquor in greenishyellow shades. The dyeings have good fastness to light and dry-heatpleating and setting.

EXAMPLE 313

The phosphorus oxychloride in Example 312 is replaced by an equivalentamount of phosphorus tribromide. 36 parts of dye (R=CH₂ CH₂ Br) isobtained having a bromine content of 17.5% (calculated 19.2%); it hassimilar tinctorial properties.

The dyes in the following Table are prepared analogously:

    ______________________________________                                                                           Material                                   Example                                                                                R             Shade       dyed                                       ______________________________________                                        Formula (I): X = Y = H                                                        314    --CH.sub.2 CH.sub.2 CH.sub.2 Cl                                                               greenish yellow                                                                           polyester                                  315    --CH.sub.2 CH.sub.2 CH.sub.2 Br                                                               "           "                                          316    --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Br                                                     "           "                                          Formula (I): X = H Y = Cl                                                     317    --CH.sub.2 CH.sub.2 Cl                                                                        yellow      "                                          318    --CH.sub.2 CH.sub.2 Br                                                                        "           "                                          319    --CH.sub.2 CH.sub.2 CH.sub.2 Cl                                                               "           "                                          320    --CH.sub.2 CH.sub.2 CH.sub.2 Br                                                               "           "                                          321    --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 Br                                                     "           "                                          ______________________________________                                    

EXAMPLE 322

36.8 parts of the dye of Example 6 is boiled in 200 parts of aceticanhydride for four hours under reflux. After cooling, the product issuction filtered, washed with acetone and dried. 36.2 parts of thecorresponding mixed anhydride is obtained (R=--CH₂ COOCOCH₃).

20.5 parts of the anhydride thus obtained is introduced into 150 partsof methyl glycol and boiled under reflux for two hours. After cooling,the precipitate is suction filtered, washed with methanol and dried.20.1 parts of the corresponding dye (R=--CH₂ COOCH₂ CH₂ OCH₃) isobtained; it dyes polyester fibers and cloth greenish yellow shadeshaving good fastness to light and dry-heat pleating and setting.

EXAMPLE 323

20.5 parts of the anhydride obtained according to Example 322 isintroduced into a mixture of 100 parts of dimethylformamide and 10 partsof 3-methoxy-propylamine and stirred for two hours at 120° C. The wholeis then diluted with 50 parts of 50% aqueous methanol, allowed to cool,suction filtered and dried. 22.1 parts of the dye having the formula ofExample 1 with R=--CH₂ CONHCH₂ CH₂ CH₂ OCH₃ is obtained which isidentical both chemically and tinctorially with the dye described inExample 7.

The following dyes are obtained analogously with Examples 322 and 323:

    __________________________________________________________________________    Example                                                                                R                  Shade   Material dyed                             __________________________________________________________________________    Formula (I): X = Y = H                                                        324  CH.sub.2 COO(CH.sub.2).sub.5 OH                                                                      greenish yellow                                                                       polyester                                 325                                                                                 ##STR126##            "       "                                         326  CH.sub.2 CONHC.sub.4 H.sub.9                                                                         "       "                                         327  CH.sub.2 CONHCH.sub.2 CH.sub.2 OH                                                                    "       "                                         328  CH.sub.2 CONH(CH.sub.2).sub.5 CN                                                                     "       "                                         329                                                                                 ##STR127##            "       "                                         330  CH.sub.2 CON(C.sub.4 H.sub.9).sub.2                                                                  "       "                                         331                                                                                 ##STR128##            "       "                                         332                                                                                 ##STR129##            "       "                                         333                                                                                 ##STR130##            "       "                                         Formula (I): X = H Y = Cl                                                     334  CH.sub.2 COOCH.sub.2 CH.sub.2 OH                                                                     yellow  "                                         335                                                                                 ##STR131##            "       "                                         336  CH.sub.2 COOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                  "       "                                         337                                                                                 ##STR132##                                                              338  CH.sub.2 CONHCH.sub.2 CH.sub.2 CH.sub.2 OH                                                           "       "                                         339  CH.sub.2 CONHCH.sub.2 CHOHCH.sub.3                                                                   "       "                                         340  CH.sub.2 CONH(CH.sub.2).sub.6 CN                                                                     "       "                                         341                                                                                 ##STR133##            "       "                                         342                                                                                 ##STR134##            "       "                                         343  CH.sub.2 CON(CH.sub.2 CH.sub.2 OH).sub.2                                                             "       "                                         344                                                                                 ##STR135##            "       "                                         __________________________________________________________________________

The following dyes are prepared analogously to Example 15:

    ______________________________________                                        Example                                                                                R               Shade    Material dyed                               ______________________________________                                        Formula (I): X = H Y = Cl                                                     345    (CH.sub.2).sub.3 COOH                                                                           yellow   polyester                                   346    (CH.sub.2).sub.3 COOCH.sub.3                                                                    "        "                                           347    (CH.sub.2).sub.3 CONHC.sub.6 H.sub.5                                                            "        "                                           348    (CH.sub.2).sub.5 COOH                                                                           "        "                                           349    (CH.sub.2).sub.5 COOC.sub.2 H.sub.5                                                             "        "                                           350    (CH.sub.2).sub.5 CONHC.sub.6 H.sub.5                                                            "        "                                           351    C.sub.2 H.sub.4 SC.sub.2 H.sub.4 OH                                                             "        "                                           352    C.sub.2 H.sub.5 SC.sub.2 H.sub.4 OCOC.sub.6 H.sub.5                                             "        "                                           353    C.sub.2 H.sub.4 SC.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                             "        "                                           354    C.sub.2 H.sub.4 SC.sub.2 H.sub.4 OCONHC.sub.6 H.sub.5                                           "        "                                           ______________________________________                                    

I claim:
 1. An azo dye of the formula: ##STR136## in which Y¹ ishydrogen, chlorine, carboalkoxy selected from the group consisting ofcarbomethoxy, carboethoxy, carbopropoxy, carbobutoxy,carbo-β-ethylhexoxy, carbo-β-hydroxyethoxy, carbo-ω-hydroxypentoxy,carbo-ω-hydroxyhexoxy, carbo-β-methoxyethoxy and carbo-β-butoxyethoxy orN-substituted carbamoyl selected from the group consisting ofN-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl,N-butylcarbamoyl, N-β-ethylhexylcarbamoyl, N-β-hydroxyethylcarbamoyl,N-β-hydroxypropylcarbamoyl, N-γhydroxypropylcarbamoyl,N-β-methoxyethylcarbamoyl, N-γ-methoxypropylcarbamoyl,N-γ-butoxypropylcarbamoyl, N-γ-(β'-ethylhexoxy)-propylcarbamoyl,N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N,N-dipropylcarbamoyl,N,N-dibutylcarbamoyl, N-methyl-N-β-hydroxyethylcarbamoyl,N,N-di-β-hydroxyethylcarbamoyl, N-benzylcarbamoyl, andN-phenylethylcarbamoyl; andR¹ is selected from the group consisting ofmethyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-hexyl,β-ethylhexyl, n-decyl, β-methylnonyl, stearyl, β-hydroxyethyl,β-methoxyethyl, γ-hydroxypropyl, β-hydroxypropyl, γ-methoxypropyl,γ-ethoxypropyl, γ-(β-ethylhexoxy)-propyl, γ-acetoxypropyl,γ-propionyloxypropyl, benzoyloxyethyl, benzoyloxypropyl,methoxyacetoxypropyl, α-methyl-β-hydroxypropyl,β-methyl-β-hydroxypentyl, ω-hydroxyhexyl, carboxymethyl orcarboxypropyl, ethoxycarbonylmethyl, methoxycarbonylpropyl,dimethylaminocarbonylmethyl, butylaminocarbonylmethyl,phenylaminocarbonylpropyl, carboxyethyl, carboxypentyl,methoxycarbonylethyl, ethoxycarbonylpentyl, diethylaminocarbonylethyl,β-ethylhexylaminocarbonylethyl, phenylaminocarbonylpentyl,acetylaminoethyl, propionylaminoethyl, acetylaminopropyl,acetylaminobutyl, propionylaminobutyl, benzoylaminobutyl,acetylaminohexyl, ω-cyanopentyl, ω-cyanohexyl,β-(β'-hydroxyethoxy)-ethyl, β-(β'-acyloxyethoxy)-ethyl and the radicalshaving the formulae: --C₂ H₄ S--C₂ H₄ OH, --C₂ H₄ S--C₂ H₄ OCOC₆ H₅,--C₂ H₄ SC₂ H₄ OCOC₂ H₅, ##STR137##